The ligand of 2,6-bis［N-(1,1’-dimethyl-2’-hydroxy)carbamoyl］pyridine and its nickel(Ⅱ) complex were synthesized and characterized by using 1H-NMR, 13C-NMR, FTIR, UV-Vis and elemental analysis, and the complex formulae of C15H21N3O4Ni·H2O were determined. The spectral property of the free ligand and its nickel(Ⅱ) complex was discussed with the comparison method, and then the structure of nickel(Ⅱ) complex was determined. The spectral analysis results show that 2,6-bis［N-(1,1’-dimethyl-2’-hydroxy)carbamoyl］pyridine acts as a tridentate ligand, coordinating through two nitrogen atoms of amide anion and one nitrogen atom of aromatic pyridine-ring, and the nickel(Ⅱ) ion is a four-coordinated geometry with dsp2 hybrid orbitals for bonding these coordinating atoms. The target complex is a square planar low-spin nickel(Ⅱ) coordination compound, and a nickel(Ⅱ) ion coordinates to a tridentate ligand and one coordination water molecule.